CN102171266B - Scratch- and weather-resistant varnish curable by means of actinic radiation or curable by heat and by means of actinic radiation - Google Patents
Scratch- and weather-resistant varnish curable by means of actinic radiation or curable by heat and by means of actinic radiation Download PDFInfo
- Publication number
- CN102171266B CN102171266B CN2009801388647A CN200980138864A CN102171266B CN 102171266 B CN102171266 B CN 102171266B CN 2009801388647 A CN2009801388647 A CN 2009801388647A CN 200980138864 A CN200980138864 A CN 200980138864A CN 102171266 B CN102171266 B CN 102171266B
- Authority
- CN
- China
- Prior art keywords
- coating composition
- acrylate
- aforementioned
- methyl
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a coating composition that can be cured by means of actinic radiation, or that can be cured by heat and by means of actinic radiation, comprising (A) at least one unsaturated urethane(meth)acrylate, and (B) at least one unsaturated melamine(meth)acrylate, wherein the ratio of the weight proportions of the components (A) and (B) is between (A):(B) = 1:1 and (A):(B) = 1:5.
Description
Technical field
The present invention relates to utilize actinic radiation or by heat with utilize the coating composition of actinic radiation curable, this coating composition has special scrape resistant and weathering resistance, and this coating composition is based on carbamate (methyl) acrylate.The invention still further relates to this coating composition for the preparation of the purposes of coating system, and relate to the base material that adopts this coating composition japanning.
Background technology
Utilize actinic radiation curable and be known based on the coating composition of carbamate (methyl) acrylate, and for example be described in the International Patent Application WO 2005/120725.They are used for the motor vehicle retouching paint at this special design.In this was used, they must stand the high request about scratch resistance and weathering resistance aspect.The scratch resistance of the coating system that is obtained by these coating compositions can be modified by improving cross-linking density as known.Yet, be usually to follow the elastic loss of the coating system of its appearance to this shortcoming.Although often show very high scratch resistance through highly cross-linked coating system, yet they are owing to not enough elasticity tends to form crackle, and therefore do not have best weathering resistance.
In Germany Patent document DE 197 09 467, also recognize the problem of elastic loss.This patent is asked for protection coating subsequently in general manner, and it it is said to have at least 10 in solid state
7.6The storage modulus E ' in the caoutchouc elasticity scope of Pa, and the dissipation factor tan δ under 20 ℃ that is 0.10 to the maximum.It is said and select described binding agent according to the physical criterion of the coating system of mentioned abundant curing.About the chemical property of described binding agent, the compounds category of wide region has only been proposed, wherein single binding agent may meet these standards of the coating system of described abundant curing.(methyl) acrylic copolymer, polyether acrylate, polyester acrylate, unsaturated polyester, epoxy acrylate, urethane acrylate, amino acrylates, trimeric cyanamide acrylate, organic silicon acrylic ester and the corresponding methacrylic ester (36-38 is capable for page 4) of (methyl) acryl official energy have for example been mentioned.Preferred use does not contain the binding agent (38-39 is capable for page 4) of aromatic structure unit.It does not comprise trimeric cyanamide (methyl) acrylate especially, owing to always have the aromatics triazine ring in this compound.Aliphatic urethane acrylates is particularly preferred.The chemical property that does not have further concrete instruction binding agent to be used.
Summary of the invention
Goal of the invention
Therefore, the purpose of this invention is to provide coating composition, it can utilize actinic radiation to solidify or by heat with utilize actinic radiation to solidify, and can obtain coating system by this coating composition, and this coating system has high scratch resistance and has simultaneously high weathering resistance.The coating that obtains also should meet for the motor vehicle coating system propose particularly about the high request of gloss, stability of gloss, chemical-resistant, anti-hitting property of stone and adhesion strength aspect.
The realization of purpose
Astoundingly, by being provided, following coating composition realized this purpose, described coating composition can utilize actinic radiation to solidify or by heat with utilize actinic radiation to solidify, this coating composition comprises (A) at least a unsaturated urethane (methyl) acrylate, (B) at least a unsaturated trimeric cyanamide (methyl) acrylate, wherein the ratio of component (A) and weight fraction (B) is at (A): (B)=1: 1 to (A): (B)=1: 5 between.
Specifically describe
Suitable unsaturated urethane (methyl) acrylate (A) is any desirable unsaturated urethane acrylate and/or unsaturated urethane methacrylic ester in principle.In this context, term " unsaturated " refers to have average at least one reactive carbon-to-carbon double bond in described molecule, for example in acrylate group.Preferred aliphatic unsaturated urethane (methyl) acrylate that uses.Suitable unsaturated urethane (methyl) acrylate can for example obtain in the following way: make the reaction of vulcabond or polyisocyanates and chainextender, described chainextender is selected from glycol/polyol and/or diamines/polyamines and/or two mercaptan/polythiol and/or alkanolamine, and then makes remaining free isocyanate groups group and the reaction of at least a (methyl) vinylformic acid hydroxyalkyl acrylate.At this, preferably the amount of chainextender, vulcabond and/or polyisocyanates and (methyl) vinylformic acid hydroxyalkyl acrylate is selected so that:
1.) the equivalent ratio of the reactive group of NCO group and described chainextender (hydroxyl, amino and/or mercapto groups) was preferably 2: 1 between 3: 1 to 1: 2, and
2.) the OH group of described (methyl) vinylformic acid hydroxyalkyl acrylate exists with following amount, and this amount is the still stoichiometric amount of free isocyanate groups about the prepolymer that is formed by isocyanic ester and chainextender.
Alternatively, can also for example prepare in the following way suitable unsaturated urethane (methyl) acrylate: at first a part and at least a (methyl) vinylformic acid hydroxyalkyl acrylate with the isocyanate groups of vulcabond or polyisocyanates reacts, and the chainextender of remaining isocyanate groups and the above-mentioned type is reacted.In addition, in this case, the amount of chainextender, isocyanic ester and (methyl) vinylformic acid hydroxyalkyl acrylate is selected so that the equivalent ratio of the reactive group of NCO group and described chainextender is 3: 1 to 1: 2, preferred 2: 1, and the equivalent ratio of the OH group of residue NCO group and described at least a (methyl) vinylformic acid hydroxyalkyl acrylate is 1: 1.
Self-evident is that all intermediate forms between these two techniques also are possible.For example, can be at first a part of isocyanate groups and the glycol of vulcabond be reacted, a part of in addition isocyanate groups and (methyl) vinylformic acid hydroxyalkyl acrylate can be reacted afterwards, remaining isocyanate groups and diamines can be reacted afterwards.
Therefore these various methods that prepare described unsaturated urethane (methyl) acrylate are known (for example EP-A-204 161) and do not need accurate description.
Described unsaturated urethane (methyl) acrylate can be for example by the prepolymer that makes corresponding isocyanate-functional and/or oligopolymer and than aliphatic diol and/or the diamines of long-chain, the aliphatic diol and/or the diamines that more preferably have at least 6 C atoms react and softnessization.This softness reaction can be carried out before or after this is adding described at least a (methyl) vinylformic acid hydroxyalkyl acrylate.
Example as suitable unsaturated urethane (methyl) acrylate (A) also can be mentioned following commercially available prod:
-
2513, derive from the unsaturated aliphatic urethane acrylate of Bayer MaterialScience company;
-
Derive from the unsaturated aliphatic urethane acrylate of Cytec company;
-
9028V derives from the unsaturated aliphatic urethane acrylate of BASF SE company.
Described at least a unsaturated urethane (methyl) acrylate (A) preferably has 1000 to 10000g/mol, more preferably 2000 to 5000g/mol weight-average molecular weight.Described weight-average molecular weight is by using polystyrene to measure as the gel permeation chromatography of standard substance.
As a rule, acrylate group is easier to reaction than methacrylate based group, so that easier reaction can occur.Therefore, described at least a unsaturated urethane (methyl) acrylate unsaturated aliphatic urethane acrylate preferably.More preferably, it is based on hexamethylene diisocyanate (HDI), wherein be preferably based on the trimeric unsaturated aliphatic urethane acrylate of HDI, and very particularly preferably be based on hexamethylene diisocyanate (HDI) and have the unsaturated aliphatic urethane acrylate of the average functionality of 2 to 3 acrylate groups of each molecule.
Suitable unsaturated trimeric cyanamide (methyl) acrylate (B) is any desirable unsaturated trimeric cyanamide acrylate and/or unsaturated trimeric cyanamide methacrylic ester in principle.Term " unsaturated " refers to have average at least one reactive carbon-to-carbon double bond in this context in described molecule, for example in acrylate group.Described at least a unsaturated trimeric cyanamide (methyl) acrylate (B) preferably has on average at least 3 (methyl) acrylate groups of each triazine ring and the more preferably functionality of average at least 4 (methyl) acrylate groups of each triazine ring.Suitable unsaturated trimeric cyanamide (methyl) acrylate can for example prepare in the following way: the direct etherificate (Veretherung) of hexamethylolmelamine (HMM) or six (methoxymethyl) trimeric cyanamide (HMMM) exchange (Umetherung) with the ether of at least a hydroxyl (methyl) acrylate, described hydroxyl (methyl) acrylate is (methyl) Hydroxyethyl Acrylate for example, (methyl) vinylformic acid hydroxy propyl ester, BDO list (methyl) acrylate or caprolactone (methyl) acrylate.
Described at least a unsaturated trimeric cyanamide (methyl) acrylate (B) preferably has 1000 to 7000g/mol, more preferably 2000 to 4500g/mol weight-average molecular weight.Described weight-average molecular weight is by using polystyrene as the gel permeation chromatography of standard substance.
As a rule, acrylate group is easier to reaction than methacrylate based group, so that easier reaction can occur.Therefore, described at least a unsaturated trimeric cyanamide (methyl) acrylate (B) is unsaturated trimeric cyanamide acrylate preferably, be more preferably the unsaturated trimeric cyanamide acrylate of the functionality with average at least 3 (methyl) acrylate groups of each triazine ring, and very particularly preferably it is the unsaturated trimeric cyanamide acrylate with functionality of average at least 4 (methyl) acrylate groups of each triazine ring.
Example as suitable unsaturated trimeric cyanamide (methyl) acrylate (B) can also be mentioned following commercially available product:
-CN890 derives from the multifunctional trimeric cyanamide acrylate of Sartomer company;
-BMM-215 derives from the trifunctional trimeric cyanamide methacrylic ester of Bomar Specialities Co. company;
-BMA-200 derives from the trifunctional trimeric cyanamide acrylate of Bomar Specialities Co. company;
-BMA-222 derives from the trifunctional trimeric cyanamide acrylate of Bomar Specialities Co. company;
-BMA-300 derives from the trifunctional trimeric cyanamide acrylate of Bomar Specialities Co. company.
According to the present invention, the ratio of component (A) and weight fraction (B) is at (A): (B)=1: 1 to (A): (B)=1: 5 between.The ratio of preferred described weight fraction is at (A): (B)=1: 1.5 to (A): (B)=1: 2.5 between, more preferably at (A): (B)=1: 1.8 to (A): (B)=1: 2.2 between.
In coating of the present invention, component (A) and (B) preferably use take following amount: [(A)+(B)] as based on 30 to 90wt% of described liquid coating composition gross weight, more preferably 50 to 70wt%.
If coating composition of the present invention is cured by means of the UV radiation, then coating composition of the present invention comprises at least a photoinitiator (C).Preferred use based on the summation meter of the reactive diluent of component (A), (B), (C) and any existence 0.1 to 5wt%, more preferably 0.5 to 3wt% at least a photoinitiator (C).Can use the photoinitiator commonly used that uses in the UV curable coating composition well known by persons skilled in the art, example is to be called with name on the market
(all deriving from CIBA Specialty Chemicals Inc.) and
The obtainable product of TPO (BASF AG company).The absorption of used photoinitiator preferably is in the wavelength region of 200-400nm.
Can also comprise one or more reactive diluents if coating composition of the present invention is suitable.These reactive diluents can be alefinically unsaturated compounds at this.Described reactive diluent for example can be list, two or polyunsaturated.Reactive diluent refers to become by chemical reaction the solvent of the integral part of described binding agent in film process.
Can also comprise one or more solvents if coating composition of the present invention is suitable, these solvents are not included in the described reactive diluent, and example is ether, ester, aliphatic series and/or aromatic hydrocarbon, more preferably dimethylbenzene, butylacetate, methylethylketone and/or ethanol.
Coating composition of the present invention can also comprise other conventional additives, example is photostabilizer (HALS compound for example, benzotriazole, benzophenone, triazine, oxalic dianilide etc.), slip additive, stopper, matting agent, defoamer, flow agent or other be generally used for the additive in the coating.The conventional amount used of additive commonly used is the 15wt% that is up to based on the gross weight meter of described coating composition, and preferred 2 to 9wt%.Coating composition of the present invention preferably comprises at least a photostabilizer.
Coating composition of the present invention is Clear paint preferably, so that it does not preferably contain filler, perhaps only contains transparent filler, and does not contain opaque pigment.Yet, also be possible to use through painted coating composition form.In this case, described coating composition contains one or more pigment of 2 to 40wt% based on the gross weight meter of described coating composition.In this case, described coating composition can also contain one or more fillers based on described coating composition gross weight meter 1 to 20wt%.In the situation of the pigment that uses higher concentration and/or filler, preferred curing is electrocuring.
The present invention also provides the purposes of coating composition of the present invention for the preparation of coating system.In order to prepare coating system, coating composition of the present invention can be applied technology by means of routine well known by persons skilled in the art and be applied on the base material to be painted.Apply can be for example by means of smear, roller coating, spraying, dipping, blade coating, roller coat, casting or injection carry out.
Applying preferably at 5-60 μ m of coating composition of the present invention, more preferably 20-50 μ m and very preferably carrying out under the dry film layer thickness of 35-45 μ m.
Coating composition of the present invention can be used for preparing the coating system of single coating or overbrushing layer.In the situation of the coating system for preparing the overbrushing layer, coating composition of the present invention can be for the preparation of subcoat, the one or more other top coat retes of coating on this subcoat perhaps can also be for the preparation of the top top coat rete of the coating system of described overbrushing layer.Coating composition of the present invention is preferred for preparing the top coating of the coating system of overbrushing layer.
Described coating composition can for the preparation of the coating on the base material to be painted of any hope, for example be used for coat metal substrates.Coating composition of the present invention is preferred for coating machine multiple unit train body and parts thereof.
Very particularly preferably, coating composition of the present invention for the preparation of the top coat system on body of motor vehicle and parts thereof, is particularly preferred for the transparent top coat system of preparation in the continuous application of motor vehicle.
In order to prepare coating at metal base, preferably be applied to coating composition of the present invention by drop priming and/or be coated with on sheet metal, sheet metal strip and/or the body of motor vehicle or its parts of basic coating.Operable priming paint is normally used priming paint.As basic coating, can use basic coating conventional basic coating and water-based, heat and/or radiation-hardenable.In addition, coating composition of the present invention can also be applied to and at first be coated with cataphoretic coating and be coated with subsequently on the metal base of floating coat and/or basic coating.Can also wet at this and to bump wet technological operation.In described technique, usually need to before applying coating composition of the present invention, toast described basic coating and/or floating coat.
To be applied to that coating composition on the described base material utilizes actinic radiation or by heat with utilize actinic radiation to be cured.
Before the curing, the dry coating composition that applies in the middle of can carrying out, described middle drying is the solvent that exists for for example flash distillation, for example carries out under 30 ℃ to 80 ℃ 5 to 30 minutes.
In the context of the present invention, the curing by thermal initiation of the rete of term " thermofixation " expression coating composition.
In the context of the present invention, the actinic radiation meaning refers to electromagnetic radiation, for example near infrared (NIR), visible light, UV radiation, X ray or gamma-radiation, especially UV radiation, and bombardment, for example electron beam, β radiation, α radiation, proton beam or neutron beam, especially electron beam.Curing by the UV radiation causes by means of free radical or cationic photosensitive initiator usually.Curing by actinic radiation is the curing by the UV radiation or the curing by electron beam preferably.
If the curing of actinic radiation is solidified and utilized to the associating use heat in the situation of coating composition of the present invention, then be also referred to as " dual cure ".
Thermofixation and utilize the curing of actinic radiation can be by means of those skilled in the art in each case for the known system of this purpose is carried out under usually known condition.For example UV solidifies and can carry out under the following conditions: utilize 100-10000mJ/cm
2UV dosage, 50-4000mW/cm
2Yield of radiation (surveying instrument: Power Puck, EIT Inc.) and＜0.2% residual oxygen.Electrocuring can for example utilize 5-15 thousand Grays' dosage to carry out.
The present invention also provides the base material that adopts coating composition japanning of the present invention, preferred body of motor vehicle or its parts.
The below will further specify the present invention by embodiment.
Embodiment
Embodiment
Embodiment 1:
The preparation of coating composition of the present invention
The the 1st to 5 that provides in will the B hurdle such as table 1 adds and under agitation is processed into uniform mixture in advance.Subsequently the 6th to 10 is under agitation added in succession.Obtain uniform mixture by further stirring.
Comparative Examples 1:
The preparation of non-coating composition of the present invention
Provide in will the A hurdle such as table 1 the 1st to 5 initial adds and under agitation is processed into uniform mixture.Subsequently the 6th to 10 is under agitation added in succession.Obtain uniform mixture by further stirring.
The preparation of coating system
To derive from the coating composition of the present invention of embodiment 1 and derive from the coating composition non-of the present invention of Comparative Examples 1 for the preparation of transparent top coat system according to following rules.
Used base material is steel plate, and this steel plate has adopted ability cathode electrophoresis coating commonly used, and (CathoGuard 500, BASF) precoating.Dry film layer thickness with 13-18 μ m on this coating applies water-based basic coating commonly used, and 80 ℃ of lower bakings 10 minutes with then 130 ℃ of lower bakings 15 minutes.Still on the same day, apply by means of spraying, with the dry film layer thickness of 40-45 μ m, the coating composition non-of the present invention that coating derives from the coating composition of the present invention of embodiment 1 or derives from Comparative Examples 1 on it.With solvent after 60 ℃ of lower flash distillations 15 minutes, carry out UV and solidify, wherein UV dosage is 4000mJ/cm
2, yield of radiation is 2000mW/cm
2(surveying instrument: Power Puck, EIT Inc.), residual oxygen＜0.1% and exposure temperature are 45 ℃.
The test of coating system and performance
The coating system that obtains has the performance that provides in to 9 at table 2.
Determine chemical-resistant (table 2) by gradient baking oven test (corresponding to DIN EN ISO 2812-5).Use in each case mentioned chemical spray coating system, and with its incubation 30 minutes under the different temperature X in each case, afterwards it was being deposited under 23 ℃ 24 hours under standard temperature and humidity condition, and in baking oven, under 80 ℃, heating 2 hours after optional.Record is educated temperature X with the highest temperature of degree centigrade expression, under this temperature, is depositing after (23 ℃ lower 24 hours) and/or after with post-heating (80 ℃ lower 2 hours), and still not having the optics visible of described coating system to damage is visible.
In order to measure scraping patience (table 3), at first measure the original gloss of described coating system from 20 ° viewing angle.Make afterwards described coating system experience according to the scraping load of DIN EN ISO 20566 DE (AMTEC abrasion resistance).After described load, described sample is also measured glossiness again with the test gasoline cleaning.The remaining glossiness that represents with % that obtains from before load and the merchant of gloss value afterwards draw.
In addition, test described scratch resistance according to the test procedure of ASTM D 6279.The results are shown in the table 4.
Hit anti-the hitting property of stone (table 5) that device checks described coating system according to DIN EN ISO 20567-1 by means of the multiple stone of VDA.
By the adhesion strength of testing (table 6) and passing through to measure according to the constant warm and humid condition test of water of condensation (KK test) (table 7) above 240 hours of DIN50017 KK described coating system according to the ball falling impact of DIN 55996-3.
In order to check the weathering resistance of described coating system, use the QUV Weathering device that derives from Q-Panel company.Form (table 8) (i.O.=is satisfied) at various time point visual assessment crackle.Measure described glossiness (table 9) at various time point from 20 ° viewing angle.
The result of test clearly illustrates that, the coating system that is obtained by coating composition of the present invention shows very high scratch resistance (table 3 and 4) and simultaneously with respect to the improved weathering resistance of conventional coating system (table 8 and 9).In addition, the coating system that is obtained by coating composition of the present invention shows with respect to the improved chemical-resistant of conventional coating system (table 2), and does not have high anti-hitting property of stone (table 5) and adhesion strength (table 6 and 7) simultaneously with changing.
Claims (28)
1. utilize actinic radiation or by heat with utilize the coating composition of actinic radiation curable, this coating composition comprises:
(A) at least a unsaturated urethane (methyl) acrylate, and
(B) at least a unsaturated trimeric cyanamide acrylate,
It is characterized in that the ratio of component (A) and weight fraction (B) is at (A): (B)=1:1 is to (A): (B)=1:5 between.
2. coating composition as claimed in claim 1 is characterized in that, the ratio of described weight fraction is at (A): (B)=1:1.5 is to (A): (B)=1:2.5 between.
3. such as aforementioned claim 1 or 2 described coating compositions, it is characterized in that described at least a unsaturated urethane (methyl) acrylate (A) is aliphatic unsaturated urethane (methyl) acrylate.
4. such as aforementioned claim 1 or 2 described coating compositions, it is characterized in that described at least a unsaturated urethane (methyl) acrylate (A) is the unsaturated urethane acrylate.
5. such as aforementioned coating composition claimed in claim 3, it is characterized in that described at least a unsaturated urethane (methyl) acrylate (A) is the unsaturated urethane acrylate.
6. such as each described coating composition in the aforementioned claim 1,2 and 5, it is characterized in that described at least a unsaturated trimeric cyanamide acrylate (B) has the functionality of on average at least 3 (methyl) acrylate groups of each triazine ring.
7. such as aforementioned coating composition claimed in claim 3, it is characterized in that described at least a unsaturated trimeric cyanamide acrylate (B) has the functionality of on average at least 3 (methyl) acrylate groups of each triazine ring.
8. such as aforementioned coating composition claimed in claim 4, it is characterized in that described at least a unsaturated trimeric cyanamide acrylate (B) has the functionality of on average at least 3 (methyl) acrylate groups of each triazine ring.
9. each described coating composition as in the aforementioned claim 1,2,5,7 and 8 is characterized in that, described coating composition can by means of the UV radiation or by heat with utilize the UV radiation to solidify, and comprise at least a photoinitiator (C).
10. as aforementioned coating composition claimed in claim 3, it is characterized in that described coating composition can be by means of the UV radiation or by heat with utilize the UV radiation to solidify, and comprises at least a photoinitiator (C).
11. as aforementioned coating composition claimed in claim 4, it is characterized in that described coating composition can by means of the UV radiation or by heat with utilize the UV radiation to solidify, and comprise at least a photoinitiator (C).
12. as aforementioned coating composition claimed in claim 6, it is characterized in that described coating composition can by means of the UV radiation or by heat with utilize the UV radiation to solidify, and comprise at least a photoinitiator (C).
13. as each described coating composition in the aforementioned claim 1,2,5,7,8,10-12, it is characterized in that described coating composition can be by means of electron beam or by heat with utilize electron beam to solidify.
14. as aforementioned coating composition claimed in claim 3, it is characterized in that, described coating composition can by means of electron beam or by heat and utilize electron beam to solidify.
15. as aforementioned coating composition claimed in claim 4, it is characterized in that, described coating composition can by means of electron beam or by heat and utilize electron beam to solidify.
16. as aforementioned coating composition claimed in claim 6, it is characterized in that, described coating composition can by means of electron beam or by heat and utilize electron beam to solidify.
17. as aforementioned coating composition claimed in claim 9, it is characterized in that, described coating composition can by means of electron beam or by heat and utilize electron beam to solidify.
18. such as each described coating composition among aforementioned claim 1,2,5,7,8,10-12, the 14-17, it is characterized in that this coating composition is Clear paint.
19. such as aforementioned coating composition claimed in claim 3, it is characterized in that this coating composition is Clear paint.
20. such as aforementioned coating composition claimed in claim 4, it is characterized in that this coating composition is Clear paint.
21. such as aforementioned coating composition claimed in claim 6, it is characterized in that this coating composition is Clear paint.
22. such as aforementioned coating composition claimed in claim 9, it is characterized in that this coating composition is Clear paint.
23. such as the described coating composition of aforementioned claim 13, it is characterized in that this coating composition is Clear paint.
24. such as the purposes of each described coating composition in the aforementioned claim 1 to 23 for the preparation of coating system.
25. purposes as claimed in claim 24 is characterized in that, described coating system is the uppermost layer of overbrushing layer coating system.
26. such as aforementioned claim 24 or 25 described purposes, it is characterized in that described coating system is the coating on body of motor vehicle or its parts.
27. adopt the base material that applies such as each described coating composition in the aforementioned claim 1 to 23.
28. base material as claimed in claim 27 is characterized in that, this base material is body of motor vehicle or its parts.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102008051472A DE102008051472A1 (en) | 2008-10-14 | 2008-10-14 | Scratch and weather resistant varnish curable with actinic radiation or thermally and with actinic radiation |
| DE102008051472.1 | 2008-10-14 | ||
| PCT/EP2009/007344 WO2010043374A1 (en) | 2008-10-14 | 2009-10-13 | Scratch- and weather-resistant varnish curable by means of actinic radiation or curable by heat and by means of actinic radiation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102171266A CN102171266A (en) | 2011-08-31 |
| CN102171266B true CN102171266B (en) | 2013-05-29 |
Family
ID=41531748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801388647A Active CN102171266B (en) | 2008-10-14 | 2009-10-13 | Scratch- and weather-resistant varnish curable by means of actinic radiation or curable by heat and by means of actinic radiation |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US8445557B2 (en) |
| EP (1) | EP2342253B1 (en) |
| JP (1) | JP2012505300A (en) |
| KR (1) | KR20110080163A (en) |
| CN (1) | CN102171266B (en) |
| DE (1) | DE102008051472A1 (en) |
| WO (1) | WO2010043374A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120130555A1 (en) * | 2010-11-23 | 2012-05-24 | Howard Jelinek | Hybrid energy cube |
| BR112020019262B1 (en) * | 2018-03-27 | 2023-12-12 | Mercene Coatings Ab | METHOD OF COATING A SUBSTRATE AND COATED SUBSTRATE |
| CN109593157B (en) * | 2018-10-31 | 2021-01-26 | 韶关市合众化工有限公司 | Melamine modified waterborne acrylic flame-retardant resin and preparation method thereof |
| US10985607B1 (en) * | 2019-08-15 | 2021-04-20 | Pedro Silva | Backup power supply system |
| US20230374342A1 (en) * | 2020-10-07 | 2023-11-23 | Daicel Corporation | Curable composition and cured product thereof |
| CN113278369B (en) * | 2021-05-25 | 2022-06-28 | 佛山禾邦新材料科技有限公司 | High-adhesion ultraviolet-curing three-proofing adhesive and preparation method thereof |
| CN117247701B (en) * | 2023-04-04 | 2024-07-30 | 广州思奇高分子材料技术有限公司 | UV-resistant silica gel paste and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0568967A2 (en) * | 1992-05-07 | 1993-11-10 | Herberts Gesellschaft mit beschränkter Haftung | Method for preparing multilayer coatings |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4609718A (en) | 1985-05-08 | 1986-09-02 | Desoto, Inc. | Ultraviolet curable buffer coatings for optical glass fiber based on long chain oxyalkylene diamines |
| JPH08217840A (en) * | 1995-02-15 | 1996-08-27 | Hitachi Chem Co Ltd | Photocurable resin composition and coating |
| DE19709467C1 (en) * | 1997-03-07 | 1998-10-15 | Basf Coatings Ag | Coating compositions and processes for producing multicoat paint systems |
| DE19920801A1 (en) * | 1999-05-06 | 2000-11-16 | Basf Coatings Ag | Highly scratch-resistant multi-layer coating, process for its production and its use |
| DE10012580A1 (en) * | 2000-03-15 | 2001-09-27 | Basf Coatings Ag | Photoinitiator free (meth)acrylate copolymer based coating agent, adhesive or sealant, comprises a (meth)acrylate copolymer or a compound that is activated by actinic radiation |
| DE10129969A1 (en) * | 2001-06-21 | 2003-01-09 | Basf Coatings Ag | Mixtures containing carbamate and / or allophanate groups, curable thermally and with actinic radiation |
| JP3960417B2 (en) * | 2001-11-06 | 2007-08-15 | アイカ工業株式会社 | TRANSFER SHEET USING ACTIVE ENERGY RAY-CURABLE RESIN COMPOSITION, PROCESS FOR PRODUCING THE SAME, AND METHOD FOR PRODUCING DECORATIVE BOARD USING THE TRANSFER SHEET |
| DE10300751A1 (en) * | 2003-01-11 | 2004-07-22 | Chemetall Gmbh | Process for coating metallic surfaces, coating composition and coatings produced in this way |
| DE10352447A1 (en) * | 2003-11-11 | 2005-06-16 | Dupont Performance Coatings Gmbh & Co Kg | Process for producing a clearcoat on motor vehicle bodies |
| US7510746B2 (en) | 2004-06-04 | 2009-03-31 | E.I. Du Pont De Nemours And Company | Process for production of multilayer coating including curing clear-coat composition with high-energy radiation |
| DE102005035980A1 (en) | 2005-07-28 | 2007-02-08 | Basf Ag | Radiation-curable binder |
-
2008
- 2008-10-14 DE DE102008051472A patent/DE102008051472A1/en not_active Withdrawn
-
2009
- 2009-10-13 EP EP09736855A patent/EP2342253B1/en not_active Not-in-force
- 2009-10-13 KR KR1020117010893A patent/KR20110080163A/en not_active Ceased
- 2009-10-13 WO PCT/EP2009/007344 patent/WO2010043374A1/en active Application Filing
- 2009-10-13 JP JP2011531389A patent/JP2012505300A/en active Pending
- 2009-10-13 US US13/124,242 patent/US8445557B2/en not_active Expired - Fee Related
- 2009-10-13 CN CN2009801388647A patent/CN102171266B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0568967A2 (en) * | 1992-05-07 | 1993-11-10 | Herberts Gesellschaft mit beschränkter Haftung | Method for preparing multilayer coatings |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010043374A1 (en) | 2010-04-22 |
| EP2342253B1 (en) | 2012-12-19 |
| US20110201720A1 (en) | 2011-08-18 |
| KR20110080163A (en) | 2011-07-12 |
| CN102171266A (en) | 2011-08-31 |
| DE102008051472A1 (en) | 2010-04-15 |
| EP2342253A1 (en) | 2011-07-13 |
| JP2012505300A (en) | 2012-03-01 |
| US8445557B2 (en) | 2013-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102171266B (en) | Scratch- and weather-resistant varnish curable by means of actinic radiation or curable by heat and by means of actinic radiation | |
| CN105949983B (en) | A kind of quick-dry type scratch resistance clear coat composition, the Preparation method and use of large arch dam | |
| US5221581A (en) | Coating composition of a glycidyl acrylic polymer, an aminoester acrylic polymer and a polyester or a polyesterurethane | |
| US5290848A (en) | Coating composition of a glycidyl acrylic polymer, an aminoester acrylic polymer and a polyester or a polyesterurethane | |
| US5064719A (en) | Coating composition of acrylic polymers containing reactive groups and an epoxy organosilane | |
| JP6866007B2 (en) | A water-based two-component clear paint composition and a method for repairing and painting a painted body using the same. | |
| CN109790277A (en) | Polyisocyantates composition, blocked polyisocyanates composition, application composition, aqueous coating composition and coating substrate | |
| NZ210597A (en) | Acrylic/polyurethane coating composition | |
| CN105764948A (en) | Coating compositions comprising a blocked isocyanate silane | |
| EP3719086B1 (en) | Acrylic polysiloxane resin coating material composition and use thereof | |
| CN104204018B (en) | Coating composition | |
| CA2849186A1 (en) | 2-component polyurethane coating on fiber cement | |
| KR102196529B1 (en) | 2-component polyurethane top coat | |
| JP6918273B1 (en) | Coating composition and method for forming a multi-layer coating film | |
| CA2675573A1 (en) | Paint compositions | |
| DK2238210T3 (en) | Paint composition | |
| EP2718342A1 (en) | Coating agent compositions, coatings made therefrom and exhibiting high scratch resistance and good polishability, and use thereof | |
| JP2022176959A (en) | Curable composition, cured product, laminate | |
| US4988759A (en) | Coating composition of acrylic polymers containing reactive groups and an epoxy organosilane | |
| JP5685505B2 (en) | Coating film for metal plating | |
| JP7315468B2 (en) | Coating composition and method for forming multi-layer coating film | |
| EP4303241B1 (en) | Uv-curable composition, hard coat and hard coated article | |
| JP7628006B2 (en) | Active energy ray curable composition for exterior building materials and use thereof | |
| JPH08253542A (en) | Vinyl copolymer resin composition, coating agent and coating film made of the coating agent | |
| JPH07238260A (en) | Antistaining coating composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |